US4066584A - Alloy fibers of rayon and copolymers of acrylic and methacrylic acids - Google Patents
Alloy fibers of rayon and copolymers of acrylic and methacrylic acids Download PDFInfo
- Publication number
- US4066584A US4066584A US05/603,483 US60348375A US4066584A US 4066584 A US4066584 A US 4066584A US 60348375 A US60348375 A US 60348375A US 4066584 A US4066584 A US 4066584A
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- United States
- Prior art keywords
- fiber
- copolymer
- cellulose
- acid
- methacrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000835 fiber Substances 0.000 title claims abstract description 86
- 229920001577 copolymer Polymers 0.000 title claims abstract description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 125000005395 methacrylic acid group Chemical class 0.000 title claims abstract description 5
- 229920000297 Rayon Polymers 0.000 title claims description 27
- 239000002964 rayon Substances 0.000 title description 8
- 239000000956 alloy Substances 0.000 title 1
- 229910045601 alloy Inorganic materials 0.000 title 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 30
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002250 absorbent Substances 0.000 claims abstract description 10
- 230000002745 absorbent Effects 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 229920002678 cellulose Polymers 0.000 claims description 14
- 239000001913 cellulose Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000009960 carding Methods 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 210000001124 body fluid Anatomy 0.000 claims description 5
- 239000010839 body fluid Substances 0.000 claims description 5
- -1 alkali metal salt Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229920003043 Cellulose fiber Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004627 regenerated cellulose Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000006069 physical mixture Substances 0.000 claims 1
- 238000009987 spinning Methods 0.000 claims 1
- 229920002125 Sokalan® Polymers 0.000 description 18
- 239000004584 polyacrylic acid Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000012530 fluid Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- 150000003839 salts Chemical group 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000011686 zinc sulphate Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000012356 Product development Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000000416 exudates and transudate Anatomy 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910004809 Na2 SO4 Inorganic materials 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920001448 anionic polyelectrolyte Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003179 starch-based polymer Polymers 0.000 description 1
- 239000004628 starch-based polymer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
- D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/225—Mixtures of macromolecular compounds
Definitions
- This application relates to highly absorbent fibers, for example, viscose rayon, hydroxypropylcellulose, and hydroxyethylcellulose, made from wood pulp or other cellulosic materials, which are useful in the production of nonwoven articles such as diapers, tampons, sanitary napkins, medical sponges, soil mulches, wiping cloths, and the like.
- Each of these applications requires a material having a high capacity for absorbing and retaining water and other aqueous fluids, particularly, body fluids.
- Cellulosic fibers have found wide use in these and similar applications because of the hydrophilic nature of the cellulose molecule and its fibrous structure which contributes integrity, form, shape, wicking ability, and liquid retention to a nonwoven material.
- alkali metal or ammonium salts of certain copolymers will further increase the absorbency and retention properties of rayon when injected into the viscose, and a fiber having a cohesiveness greater than the prior art materials referred to above can be produced.
- the cohesiveness is extremely important from the standpoint of handling staple fibers in carding equipment prior to the manufacture of finished articles of commerce from the fiber.
- the copolymers of the invention exhibit increased cohesiveness over polyacrylic acid.
- One factor generally believed to be important in fiber cohesion is the amount of crimp in the fiber.
- both the copolymers of this invention and polyacrylic acid give decreased crimp as the amount of material incorporated into the fiber is increased.
- Another factor believed to be important in fiber cohesion is the surface bonding properties of the fiber. This surface bonding, which is present in ordinary cellulose, is thought to be due to hydrogen bonding and possibly the stiffness of the fiber. Surface bonding is thought to be the predominating effect exhibited in the invention, possibly due to the higher glass transition temperature (Tg) of the copolymer imparted by methacrylic acid.
- Tg glass transition temperature
- alkali metal and ammonium salts of copolymers of acrylic and methacrylic acid incorporated into the viscose solution improves the absorbency and fluid retention properties of the resulting fiber and, most unexpectedly, cause the fiber spun from the viscose to retain its cohesiveness to such an extent that the fibers can be easily processed on carding equipment, whereas the previously mentioned fibers incorporating equal amounts of the sodium salt of polyacrylic acid, did not card satisfactorily on conventional carding equipment.
- the fibers of the invention can be prepared by adding, at any stage of viscose aging, but preferably by injecting into the fully ripened viscose solution, an amount of copolymer in the range of 2 to about 40% by weight of cellulose in the viscose solution (hereafter all percentages are given on this basis and referred to as CIV). We prefer the range of 10-20% CIV, based on a balance between increasing absorbency, economic factors, and processing conditions. The viscose solution containing the copolymer is then spun or extruded through spinneret openings into an acid bath where the cellulose fiber is regenerated.
- the regenerated fiber is stretched in air from 0-100%, or even higher, if desired, preferably from about 30 to 50% and then run through a hot aqueous bath which can be maintained at a temperature of from ambient to 100° C., preferably from 90°-97° C.
- the hot aqueous bath contains various amounts of dilute sulfuric acid, ZnSO 4 and sodium sulfate.
- the fiber is subjected to a second stretching of from 0 to 100% in the hot bath.
- the total stretch in both steps is preferably in the range of 50-70%.
- the stretching imparts the necessary strength to the finished fiber.
- the fibers, now a large bundle of continuous filaments or tow, from the combined output of a number of spinnerets is cut into short fibers of any desired length and washed and dried to a moisture content of around 11% and baled.
- the copolymer occluded in the fiber will be in acid form.
- the copolymer must be in the form of the alkali metal or ammonium salt in order to achieve the highest degree of absorbency.
- the copolymer of acrylic acid and methacrylic acid is converted to the salt form during an alkaline sodium sulfide wash bath which is conventionally used to remove metal and sulfur impurities.
- a conventional finish such as a surfactant, may be applied and the staple fiber is dried in a continuous drier to a predetermined moisture content suited to the particular end use of the fiber.
- the fiber can then be baled or carded for processing into one of the final products mentioned previously.
- a particularly suitable use for the fiber of the invention is for tampons, which may be made, for example, by one of the methods referred to in U.S. Pat. No. 3,699,965, or by other well-known methods.
- the copolymers of the invention may be prepared by known methods. In the simplest terms, an amount each of monomeric acrylic acid and methacrylic acid, calculated to give the desired average ratio in the copolymer are mixed together with a polymerization initiator in a reaction vessel and allowed to react until polymerization is completed. Special techniques well-known to those skilled in the art, such as the use of chain transfer agents and other molecular weight regulators, cross-linking agents, surfactants, redox system, controlled monomer addition, and the like, can also be applied to make specialized polymers. A copolymer containing 50% each of units derived from acrylic acid and methacrylic acid is preferred, but ratios from 90:10 (acrylic acid/methacrylic acids) to 10:90 are useful.
- the viscosity of the copolymer is an indication of the degree of polymerization (D.P.) and the molecular weight of the copolymer.
- D.P. degree of polymerization
- a wide range of D.P. values has been found to work and the major limitation on D.P. is the processing conditions.
- a copolymer having a higher molecular weight will generally be retained to a greater degree in the fiber, but if the copolymer is to be injected into the viscose, the molecular weight is limited by the viscosity which can be pumped.
- pumping systems are generally available which can handle fluids at viscosities of 10,000 cps and over.
- Copolymers of a wide range of viscosities can be used if the copolymer is added to the dissolver.
- the absorbency of the fibers can be determined by various test methods.
- a common measure of absorbency is the Water Retention Value or Secondary Swelling ("Q") which is determined in the manner disclosed in Ser. No. 330,378 referred to above and is hereby incorporated by reference. Briefly, the test measures the amount of water retained by the fiber after centrifuging for 15 minutes at 2500-3000 times gravity from which the percentage of water retained in the sample is calculated (based on dry weight by the fiber sample). A more recent test which correlates well with actual end use evaluations has been developed. The so-called Demand Wettability Test (Lichstein, Bernard, International Nonwovens and Disposables Association, 2nd Annual Symposium on Non-Woven Product Development, Mar. 5-6, 1974, Washington, D.
- a solution of a 90/10 copolymer of acrylic acid and methacrylic acid was prepared and injected into a viscose solution at a concentration of 5% CIV, thoroughly mixed with the viscose and spun into a conventional acid spinbath containing 8.5% sulfuric acid, 5.0% of MgSO 4 , 3.0% of ZnSO 4 , 18.2% of Na 2 SO 4 and 30-35 ppm laurylpyridinium chloride (LPC) at 49°-51° C. to coagulate and regenerate the cellulose to give an 1100 denier yarn containing 480 filaments. The resulting yarn was then run through a fresh hot water bath at 93°-95° C. and stretched 37% in the bath.
- LPC laurylpyridinium chloride
- the yarn was then collected in a pot in cake form, washed at 30° C. for 40 minutes at 52° C. in 0.50% aqueous sodium sulfide containing 0.05-0.10 sodium hydroxide, for 80 minutes at 30° C. in water, for 40 minutes at 30° C. in 0.01% acetic acid, for 40 minutes at 40° C. in 0.2% solution of an emulsified mineral oil controlled to a pH of 7 to 8, hydroextracted for 4.5 minutes, and dried at 70°-80° C. overnight.
- a solution of a homopolymer of acrylic acid (Rohm and Haas Acrysol A-1) was partially neutralized to a pH of 5.2 before injecting into a viscose solution at a concentration of 10% CIV, thoroughly mixed with the viscose and spun into a conventional acid spinbath containing about 5% sulfuric acid, about 20% sodium sulfate, about 1% zinc sulfate and 25 ppm lauryl pyridinium chloride at 56°-58° C. to coagulate and regenerate the cellulose to give a 22,488 denier fiber tow containing 7,496 filaments.
- the resulting tow was stretched 40% in air, run through a second bath at 92°-97° C.
- a finish solution consisting of a 0.30% aqueous solution of sorbitan monoleate and ethoxylated stearic acid was applied before the fibers were dried for about 1/2 hour in a continuous oven set at about 80° C., for about 1/2 hour at about 70° C., and for about another 1/2 hour at about 50° C. The final moisture content was about 11%. Additional samples of fiber were prepared in the same manner, but using a homopolymer of polymethacrylic acid and a 50/50 by weight copolymer of acrylic acid and methacrylic acid. The various samples are given in the table below and results of the tests for Water Retention and Saline Retention (using a 1% by weight sodium chloride solution in place of water) are set forth.
- Fibers prepared in the same manner as Example 2 containing 5 and 10% CIV polyacrylic acid, 5 and 10% CIV of a 90/10 weight ratio of a copolymer of acrylic and methacrylic acid, and 5 and 10% of a 50/50 weight ratio of a copolymer of acrylic and methacrylic acid were evaluated in the Demand Wettability Test using the general procedure described in the test method and the external pressure and solutions described below.
- Example 3 The three fibers of Example 3 containing 10% CIV of the three different polymers were carded, made into tampons and tested in the Syngina Device described by G. W. Rapp in his paper entitled "A comparison of The Absorptive Efficienty Of The Commercial Catamenial Tampons", published June, 1958, by the Department of Research, Loyola University, Chicago, Ill.
- the test fluid used was synthetic exudate described in U.S. Pat. No. 3,589,364 and consisting of 1% sodium chloride, 0.4% sodium carbonate, 10.0% glycerine, 0.46% carboxymethylcellulose and 88.14% distilled water.
- Example 3 The fibers of Example 3 containing 10% CIV polyacrylic acid and 10% CIV of a 50/50 by weight copolymer of acrylic and methacrylic acid were carded into a fiber batt. Discs were made by compressing and heating three grams of these fibers in a one-inch diameter tube. These discs were then tested in the Demand Wettability Test using about 0.2 psi external weight and a 1% sodium chloride solution as the test fluid. The average values of 15 separate evaluations are shown in the following table.
- Fibers were prepared in the same manner as Example 2 containg 15% and 20% CIV of a 50/50 weight ratio of a copolymer of acrylic acid and methacrylic acid.
- the retention values in water (WRV), saline (SRV), and synthetic exudate (ERVO (described in Example 4) are shown in the following table.
- Fibers were prepared in the same manner as in Example 2 containing 15% CIV of 75:25, 50:50, 25:75, and 10:90 weight ratio of acrylic acid and methacrylic acid.
- the Water and Saline Retention Values are shown in the following table.
- Fibers prepared in the same manner as in Example 2 and containing 10, 15, and 20% CIV polyacrylic acid and 10, 15, and 20% CIV of a 50/50 weight ratio of copolymer of acrylic and methacrylic acid were carded on a conventional 40-inch flat top card at a speed of 16 pounds per hour to give a sliver weight of 65 grains per yard.
- Example 2 It is clear from the results in Example 1 that the copolymers containing various ratios of acrylic acid to methacrylic acid have significantly increased water retention values over regular rayon. Another interesting feature of this example is the apparent decrease in water retention value as the amount of methacrylic acid in the copolymer is increased. This superiority in water retention value for polyacrylic acid over polymethacrylic acid is demonstrated clearly in Example 2. This difference is not unexpected if one considers that the water retention value is related to the swelling of the fiber and that the swelling of an anionic polyelectrolyte network, such as polyacrylic acid or a copolymer of polyacrylic acid and polymethacrylic acid, is proportional to the degree of ionization of the polyelectrolyte.
- an anionic polyelectrolyte network such as polyacrylic acid or a copolymer of polyacrylic acid and polymethacrylic acid
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- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
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Abstract
Highly absorbent, cardable cellulosic fibers are made by incorporating therein, an alkali metal or ammonium salt of a copolymer of acrylic acid and methacrylic acid, where the ratio of acrylic acid units to methacrylic acid units (by weight) is from 90:10 to 10:90.
Description
This application relates to highly absorbent fibers, for example, viscose rayon, hydroxypropylcellulose, and hydroxyethylcellulose, made from wood pulp or other cellulosic materials, which are useful in the production of nonwoven articles such as diapers, tampons, sanitary napkins, medical sponges, soil mulches, wiping cloths, and the like. Each of these applications requires a material having a high capacity for absorbing and retaining water and other aqueous fluids, particularly, body fluids. Cellulosic fibers have found wide use in these and similar applications because of the hydrophilic nature of the cellulose molecule and its fibrous structure which contributes integrity, form, shape, wicking ability, and liquid retention to a nonwoven material.
Some examples of attempts to increase the absorbency of rayon fibers can be found in U.S. application Ser. No. 330,378, filed Feb. 7, 1973, and U.S. Pat. No. 3,844,287 where alkali metal and ammonium salts of polyacrylic acid are incorporated in regenerated cellulose to increase the fluid absorbency of rayon fibers produced therefrom. Other examples of hydrophilic polymers incorporated into viscose to increase the hydrophilic properties of the fiber are the addition of carboxymethylcellulose and carboxyethyl starch as described in U.S. Pat. Nos. 3,423,167 and 3,847,636, respectively.
It has been previously known that the water absorption of a material depended upon the degree of hydrophilicity it exhibited. Such determinations of water absorption as swelling and water retention under centrifugation can be considered to be dependent on the degree of ionization of the material. Hence, the more strongly acidic that a material incorporated in a fiber is, the more absorptive it will be. In the case of polyacrylic acid, since it is more acidic, i.e., more highly ionized, than polymethacrylic acid, it would be expected that rayon fibers containing injected polyacrylic acid would have a higher water retention value than fibers containing injected polymethacrylic acid. This has been demonstrated, as will be shown later.
One problem that has been found with the approach of incorporating the anionic hydrophilic polymers into cellulosic fibers is the adverse effect on carding properties. An important property which fibers must have to be used in the applications previously mentioned, and especially in the preparation of tampons, is the capability of being carded on conventional carding equipment. The incorporation of polyacrylic acid into viscose rayon fibers by the injection method was found to decrease the sliver cohesiveness significantly. The cohesiveness property is very important in the commercial processing of rayon fibers into useful products such as tampons. If the cohesiveness is too low, then the fibrous material will not cohere, necessitating a reduction in processing speed or other process modifications, or even making the fiber impossible to process. Therefore, it is a primary object of this invention to provide a rayon fiber having improved fluid absorption without an excessive loss in fiber cohesiveness and consequent difficulty in carding the fibers for processing into useful articles.
It has now been discovered that alkali metal or ammonium salts of certain copolymers will further increase the absorbency and retention properties of rayon when injected into the viscose, and a fiber having a cohesiveness greater than the prior art materials referred to above can be produced. The cohesiveness is extremely important from the standpoint of handling staple fibers in carding equipment prior to the manufacture of finished articles of commerce from the fiber. It is now known why the copolymers of the invention exhibit increased cohesiveness over polyacrylic acid. One factor generally believed to be important in fiber cohesion is the amount of crimp in the fiber. However, both the copolymers of this invention and polyacrylic acid give decreased crimp as the amount of material incorporated into the fiber is increased. Another factor believed to be important in fiber cohesion is the surface bonding properties of the fiber. This surface bonding, which is present in ordinary cellulose, is thought to be due to hydrogen bonding and possibly the stiffness of the fiber. Surface bonding is thought to be the predominating effect exhibited in the invention, possibly due to the higher glass transition temperature (Tg) of the copolymer imparted by methacrylic acid.
Applicants have found that alkali metal and ammonium salts of copolymers of acrylic and methacrylic acid incorporated into the viscose solution improves the absorbency and fluid retention properties of the resulting fiber and, most unexpectedly, cause the fiber spun from the viscose to retain its cohesiveness to such an extent that the fibers can be easily processed on carding equipment, whereas the previously mentioned fibers incorporating equal amounts of the sodium salt of polyacrylic acid, did not card satisfactorily on conventional carding equipment.
The fibers of the invention can be prepared by adding, at any stage of viscose aging, but preferably by injecting into the fully ripened viscose solution, an amount of copolymer in the range of 2 to about 40% by weight of cellulose in the viscose solution (hereafter all percentages are given on this basis and referred to as CIV). We prefer the range of 10-20% CIV, based on a balance between increasing absorbency, economic factors, and processing conditions. The viscose solution containing the copolymer is then spun or extruded through spinneret openings into an acid bath where the cellulose fiber is regenerated. The regenerated fiber is stretched in air from 0-100%, or even higher, if desired, preferably from about 30 to 50% and then run through a hot aqueous bath which can be maintained at a temperature of from ambient to 100° C., preferably from 90°-97° C. The hot aqueous bath contains various amounts of dilute sulfuric acid, ZnSO4 and sodium sulfate. The fiber is subjected to a second stretching of from 0 to 100% in the hot bath. The total stretch in both steps is preferably in the range of 50-70%. The stretching, as is well known, imparts the necessary strength to the finished fiber. The fibers, now a large bundle of continuous filaments or tow, from the combined output of a number of spinnerets is cut into short fibers of any desired length and washed and dried to a moisture content of around 11% and baled.
After the fiber is regenerated in the acid bath, the copolymer occluded in the fiber will be in acid form. The copolymer must be in the form of the alkali metal or ammonium salt in order to achieve the highest degree of absorbency. The copolymer of acrylic acid and methacrylic acid is converted to the salt form during an alkaline sodium sulfide wash bath which is conventionally used to remove metal and sulfur impurities. In some instances, it may be desirable, particularly, if an acid wash follows the sulfide, to treat the fiber with a base such as a dilute solution of sodium bicarbonate, sodium hydroxide, and the like, to complete the conversion, and insure that a high percentage of the copolymer is in the salt form. It may be necessary to limit the amount of conversion to the salt form for certain applications where the material may come into contact with the body, since a pH which is much higher than 7 to 7.5 can cause irritation of delicate membranes and serves to promote the growth of harmful microorganisms. Finally, a conventional finish, such as a surfactant, may be applied and the staple fiber is dried in a continuous drier to a predetermined moisture content suited to the particular end use of the fiber.
The fiber can then be baled or carded for processing into one of the final products mentioned previously. A particularly suitable use for the fiber of the invention is for tampons, which may be made, for example, by one of the methods referred to in U.S. Pat. No. 3,699,965, or by other well-known methods.
The copolymers of the invention may be prepared by known methods. In the simplest terms, an amount each of monomeric acrylic acid and methacrylic acid, calculated to give the desired average ratio in the copolymer are mixed together with a polymerization initiator in a reaction vessel and allowed to react until polymerization is completed. Special techniques well-known to those skilled in the art, such as the use of chain transfer agents and other molecular weight regulators, cross-linking agents, surfactants, redox system, controlled monomer addition, and the like, can also be applied to make specialized polymers. A copolymer containing 50% each of units derived from acrylic acid and methacrylic acid is preferred, but ratios from 90:10 (acrylic acid/methacrylic acids) to 10:90 are useful.
The viscosity of the copolymer is an indication of the degree of polymerization (D.P.) and the molecular weight of the copolymer. A wide range of D.P. values has been found to work and the major limitation on D.P. is the processing conditions. For example, a copolymer having a higher molecular weight will generally be retained to a greater degree in the fiber, but if the copolymer is to be injected into the viscose, the molecular weight is limited by the viscosity which can be pumped. However, pumping systems are generally available which can handle fluids at viscosities of 10,000 cps and over. Copolymers of a wide range of viscosities can be used if the copolymer is added to the dissolver.
The absorbency of the fibers can be determined by various test methods. A common measure of absorbency is the Water Retention Value or Secondary Swelling ("Q") which is determined in the manner disclosed in Ser. No. 330,378 referred to above and is hereby incorporated by reference. Briefly, the test measures the amount of water retained by the fiber after centrifuging for 15 minutes at 2500-3000 times gravity from which the percentage of water retained in the sample is calculated (based on dry weight by the fiber sample). A more recent test which correlates well with actual end use evaluations has been developed. The so-called Demand Wettability Test (Lichstein, Bernard, International Nonwovens and Disposables Association, 2nd Annual Symposium on Non-Woven Product Development, Mar. 5-6, 1974, Washington, D. C.), uses a novel apparatus which allows the measure of volume and rate of absorption of a fluid by maintaining the absorbent material at a zero hydrostatic head so that wetting occurs purely on demand by the absorbent material. Thus, the absorption of liquid occurs only by virtue of the ability of the absorbent material to imbibe liquid with the flow of liquid abruptly stopping at the point of saturation. Variations in the method can be made to allow for end product simulation, e.g., the fibrous mass can be compressed to simulate a tampon. Testing of the compressed fiber can then be conducted on the apparatus using a variety of external pressures and testing fluids.
To satisfactorily process fibers into useful products such as tampons or other nonwoven products, it is necessary to align the fibers predominantly in one direction, prior to making the product, often accomplished by carding the fibers. The ability to card the fiber is dependent on the cohesiveness of the fibers, that is, the ability of individual fibers to "cohere together" and permit the sliver or web to be handled without breaking the cohesive mass apart. The cohesion test performed by applicant on the carded fiber is to simply measure the force in grams required to break or separate a carded sliver. The sliver cohesion factor is expressed in terms of grams of force required per grain of fiber.
To illustrate the invention, the following examples were prepared.
A solution of a 90/10 copolymer of acrylic acid and methacrylic acid was prepared and injected into a viscose solution at a concentration of 5% CIV, thoroughly mixed with the viscose and spun into a conventional acid spinbath containing 8.5% sulfuric acid, 5.0% of MgSO4, 3.0% of ZnSO4, 18.2% of Na2 SO4 and 30-35 ppm laurylpyridinium chloride (LPC) at 49°-51° C. to coagulate and regenerate the cellulose to give an 1100 denier yarn containing 480 filaments. The resulting yarn was then run through a fresh hot water bath at 93°-95° C. and stretched 37% in the bath. The yarn was then collected in a pot in cake form, washed at 30° C. for 40 minutes at 52° C. in 0.50% aqueous sodium sulfide containing 0.05-0.10 sodium hydroxide, for 80 minutes at 30° C. in water, for 40 minutes at 30° C. in 0.01% acetic acid, for 40 minutes at 40° C. in 0.2% solution of an emulsified mineral oil controlled to a pH of 7 to 8, hydroextracted for 4.5 minutes, and dried at 70°-80° C. overnight.
Additional samples of fiber were prepared in the same manner, but using 80:20 and 50:50 (weight ratio) copolymers of acrylic acid and methacrylic acid. In the table below, the water retention values of the fibers are compared to the same fiber without added copolymer.
______________________________________
Viscosity
% Solids
(Brook-
Water
Calculated
field) Retention
Polymer % As Spindle
Valve
Added pH Solids Free Acid
No. 2 (g/g)*
______________________________________
None -- -- -- -- 0.97
90/10 Acrylic
5.6 -- 19.44 3750 1.36
Acid/Methacrylic
Acid (AA/MAA)
80/20 Acrylic
5.4 -- 25.08 1400 1.30
Acid/Methacrylic
Acid
50/50 Acrylic
5.0 -- 21.32 2150 1.27
Acid/Methacrylic
Acid
______________________________________
*grams of water retained per gram of fiber
A solution of a homopolymer of acrylic acid (Rohm and Haas Acrysol A-1) was partially neutralized to a pH of 5.2 before injecting into a viscose solution at a concentration of 10% CIV, thoroughly mixed with the viscose and spun into a conventional acid spinbath containing about 5% sulfuric acid, about 20% sodium sulfate, about 1% zinc sulfate and 25 ppm lauryl pyridinium chloride at 56°-58° C. to coagulate and regenerate the cellulose to give a 22,488 denier fiber tow containing 7,496 filaments. The resulting tow was stretched 40% in air, run through a second bath at 92°-97° C. containing 3.2% sulfuric acid and about 6.15% total salts (NaSO4 + ZnSO4) and stretched 18% in the bath. The tow was then cut into 1 9/16 inches staple fiber lengths. The staple was then washed with water, then with 0.30% sodium sulfide solution, followed with water, than with a 0.175% sulfuric acid solution, followed with water, and then followed by a 0.20% sodium bicarbonate wash. A finish solution consisting of a 0.30% aqueous solution of sorbitan monoleate and ethoxylated stearic acid was applied before the fibers were dried for about 1/2 hour in a continuous oven set at about 80° C., for about 1/2 hour at about 70° C., and for about another 1/2 hour at about 50° C. The final moisture content was about 11%. Additional samples of fiber were prepared in the same manner, but using a homopolymer of polymethacrylic acid and a 50/50 by weight copolymer of acrylic acid and methacrylic acid. The various samples are given in the table below and results of the tests for Water Retention and Saline Retention (using a 1% by weight sodium chloride solution in place of water) are set forth.
__________________________________________________________________________
Viscosity
% Solids
(Brookfield)
Water Saline
% Calculated
Spindle
Retention
Retention
Polymer Added
pH
Solids
As Free Acid
No. 2 Value (g/g)
Value (g/g)
__________________________________________________________________________
Polyacrylic Acid
5.2
27.8
20.9 488 1.26 1.11
50/50 Acrylic Acid/
5.2
26.3
20.9 1300 1.12 0.99
Methacrylic Acid
Polymethacrylic
8.3
31.6
22.9 200 1.04 0.93
Acid
__________________________________________________________________________
Fibers prepared in the same manner as Example 2 containing 5 and 10% CIV polyacrylic acid, 5 and 10% CIV of a 90/10 weight ratio of a copolymer of acrylic and methacrylic acid, and 5 and 10% of a 50/50 weight ratio of a copolymer of acrylic and methacrylic acid were evaluated in the Demand Wettability Test using the general procedure described in the test method and the external pressure and solutions described below.
__________________________________________________________________________
% Viscosity
1% Sodium Chloride
Solids (Brookfield)
Solution Synthetic
% Calculated
Spindle
0.1psi
0.2psi
0.3psi
Urine*
Additive pH
Solids
As Free Acid
No. 2 (ml/g)+
(ml/g)
(ml/g)
0.1 psi
__________________________________________________________________________
5% CIV Poly-
4.4
27.5
22.0 2550 18.3 16.4
-- --
acrylic Acid
5% CIV 90/10
5.0
27.4
21.2 3000 17.7 16.6
-- --
AA/MAA
5% CIV 50/50
5.0
26.7
21.7 1837 18.9 17.5
-- --
AA/MAA
10% CIV Poly-
4.4
27.5
22.0 2550 16.3 14.6
14.9
16.6
acrylic Acid
10% CIV 90/10
5.3
27.4
21.0 2800 17.9 15.3
15.4
15.6
AA/MAA
10% CIV 50/50
5.2
26.3
20.9 1300 17.6 15.8
15.7
17.5
AA/MAA
__________________________________________________________________________
+ml/g = ml. of fluid absorbed per gram of
*Described by Weaver, Fanta, and Doane in "Highly Absorbent Starch Based
Polymers" presented at International Nonwovens Disposable Association
(INDA) 2nd Annual Symposium on Nonwoven Product Development, March 5 and
6, 1974, Washington, D. C., consisting of 97.09% distilled water, 1.94%
urea, 0.8% NaCl, 0.11% MgSO.sub. 4 . 7H.sub.2 O.sub.2, and 0.06%
CaCl.sub.2.
The three fibers of Example 3 containing 10% CIV of the three different polymers were carded, made into tampons and tested in the Syngina Device described by G. W. Rapp in his paper entitled "A comparison of The Absorptive Efficienty Of The Commercial Catamenial Tampons", published June, 1958, by the Department of Research, Loyola University, Chicago, Ill. The test fluid used was synthetic exudate described in U.S. Pat. No. 3,589,364 and consisting of 1% sodium chloride, 0.4% sodium carbonate, 10.0% glycerine, 0.46% carboxymethylcellulose and 88.14% distilled water.
The results of this test are described in the following table. The values are the average of five tests.
______________________________________
Fluid
Absorbed
Additive (g/g)
______________________________________
None 4.70
Polyacrylic Acid 5.48
50/50 Acrylic/ 5.62
Methacrylic
______________________________________
The fibers of Example 3 containing 10% CIV polyacrylic acid and 10% CIV of a 50/50 by weight copolymer of acrylic and methacrylic acid were carded into a fiber batt. Discs were made by compressing and heating three grams of these fibers in a one-inch diameter tube. These discs were then tested in the Demand Wettability Test using about 0.2 psi external weight and a 1% sodium chloride solution as the test fluid. The average values of 15 separate evaluations are shown in the following table.
______________________________________
Polymer Added Fluid Absorbed (g/g)
______________________________________
Polyacrylic Acid 6.2
50/50 Acrylic/Methacrylic Acid
6.4
______________________________________
Fibers were prepared in the same manner as Example 2 containg 15% and 20% CIV of a 50/50 weight ratio of a copolymer of acrylic acid and methacrylic acid. The retention values in water (WRV), saline (SRV), and synthetic exudate (ERVO (described in Example 4) are shown in the following table.
__________________________________________________________________________
Viscosity
% Solids
(Brookfield)
Polymer % Calculated
Spindle
WRV SRV
ERV
Additive
pH
Solids
As Free Acid
No. 2 (g/g)
(g/g)
(g/g)
__________________________________________________________________________
None 0.77
0.76
0.55
15% CIV 50/50
5.1
27.8
21.7 1475
AA/MAA 1.28
1.10
1.04
20% CIV 50/50
5.1
27.8
21.7 1475
AA/MAA 1.37
1.18
1.07
__________________________________________________________________________
Fibers were prepared in the same manner as in Example 2 containing 15% CIV of 75:25, 50:50, 25:75, and 10:90 weight ratio of acrylic acid and methacrylic acid. The Water and Saline Retention Values are shown in the following table.
__________________________________________________________________________
Viscosity
% Solids
(Brookfield)
Polymer % Calculated
Spindle
Additive pH Solids
As Free Acid
No. 2 WRV SRV
__________________________________________________________________________
75/25 AA/MAA
5.5 29.3
19.7 3075 1.41
1.20
50/50 AA/MAA
13.0
26.9
15.9 2950 1.37
1.14
50/50 AA/MAA
5.5 25.6
21.3 1775 1.33
1.12
25/75 AA/MAA
5.8 25.6
20.0 3950 1.28
1.11
10/90 AA/MAA
5.6 31.8
28.4 1000 1.11
1.01
None 0.77
0.76
__________________________________________________________________________
Fibers prepared in the same manner as in Example 2 and containing 10, 15, and 20% CIV polyacrylic acid and 10, 15, and 20% CIV of a 50/50 weight ratio of copolymer of acrylic and methacrylic acid were carded on a conventional 40-inch flat top card at a speed of 16 pounds per hour to give a sliver weight of 65 grains per yard.
The sliver cohesion values are given in the following table:
______________________________________
Sliver Cohesion (g/gr.)*
Amount of Polymer
Polyacrylic 50/50 Acrylic/
Added (CIV) Acid Methacrylid acid
______________________________________
10% 5.3 7.9
15% 4.8 7.4
20% 5.5 13.8
None 7.9
______________________________________
*Grams per grain of fibers.
All Viscosites given in the above examples are measured with a Brookfield Viscometer with a Spindle No. 2.
It is clear from the results in Example 1 that the copolymers containing various ratios of acrylic acid to methacrylic acid have significantly increased water retention values over regular rayon. Another interesting feature of this example is the apparent decrease in water retention value as the amount of methacrylic acid in the copolymer is increased. This superiority in water retention value for polyacrylic acid over polymethacrylic acid is demonstrated clearly in Example 2. This difference is not unexpected if one considers that the water retention value is related to the swelling of the fiber and that the swelling of an anionic polyelectrolyte network, such as polyacrylic acid or a copolymer of polyacrylic acid and polymethacrylic acid, is proportional to the degree of ionization of the polyelectrolyte. If one considers that the degree of ionization of polyacrylic acid is greater than the degree of ionization of polymethacrylic acid, the results in Examples 1 and 2 are not unexpected. However, the water retention value is not the only factor that determines the performance of an absorbent material. There are many test methods in the literature that attempt to measure the performance of fibers under simulated end use conditions. Evaluation of fibers containing the copolymers of the invention by the Demand Wettability and Syngina methods in Examples 3, 4, and 5 show that the copolymers of acrylic acid and methacrylic acid actually exhibit greater absorbency values than polyacrylic acid. A ready explanation of this rather unexpected result is not available at this time. It is apparent, however, that a mechanism other than the ionization of the carboxylic acid group is now affecting the absorbency properties of the fiber in certain end use performance areas.
Claims (9)
1. A highly absorbent cellulosic fiber containing in a physical admixture with cellulose from 2% to about 40% of an alkali metal salt or ammonium salt of a copolymer of acrylic acid and methacrylic acid based on the weight of cellulose, the ratio of acrylic acid to methacrylic acid in the copolymer being from 90:10 to 10:90 by weight.
2. The article of claim 1 in the form of a tampon.
3. The fiber of claim 1 wherein the cellulose is regenerated from a viscose solution.
4. The fiber of claim 1 wherein the ratio of acrylic acid to methacrylic acid is 50:50 by weight.
5. A staple cellulose fiber having improved absorbency for body fluids and improved carding characteristics and adapted to be used in making non-woven absorbent articles which are to be associated with the body for the absorption of body fluids, said fiber containing in admixture with cellulose from 2 to about 40% of an alkali metal or ammonium salt of a copolymer of acrylic acid and methacrylic acid, based on the weight of the cellulose, the ratio of acrylic acid to methacrylic acid in the copolymer being from 90:10 to 10:90 by weight.
6. The fiber of claim 5 wherein the cellulose is regenerated from a viscose solution.
7. An article of manufacture comprising highly absorbent fibers having a matrix of regenerated cellulose and from 2 to about 40% of an alkali metal or ammonium salt of a copolymer of acrylic acid and methacrylic acid in physical mixture with the cellulose, the ratio of acrylic acid to methacrylic acid units in the copolymer being from 90:10 to 10:90 by weight.
8. The article of claim 7 wherein the said ratio is 50:50 by weight.
9. A method for improving the absorbency and fluid retention of a regenerated cellulose fiber for body fluids which comprises mixing with a viscose solution from 2 to about 40%, based on the weight of cellulose in the solution, of an alkali metal salt or ammonium salt of a copolymer of acrylic acid or methacrylic acid and spinning the mixture under conditions which avoid chemical reaction of the copolymer with the cellulose to form a fiber having an absorbency for body fluids which is greater than that of a fiber made from the same viscose solution without the copolymer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/603,483 US4066584A (en) | 1975-08-11 | 1975-08-11 | Alloy fibers of rayon and copolymers of acrylic and methacrylic acids |
| GB33369/76A GB1529493A (en) | 1975-08-11 | 1976-08-11 | Cellulosic fibres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/603,483 US4066584A (en) | 1975-08-11 | 1975-08-11 | Alloy fibers of rayon and copolymers of acrylic and methacrylic acids |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/866,797 Continuation-In-Part US4240937A (en) | 1978-01-03 | 1978-01-03 | Alloy fibers of rayon and an alkali metal or ammonium salt of an azeotropic copolymer of polyacrylic acid and methacrylic acid having improved absorbency |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4066584A true US4066584A (en) | 1978-01-03 |
Family
ID=24415628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/603,483 Expired - Lifetime US4066584A (en) | 1975-08-11 | 1975-08-11 | Alloy fibers of rayon and copolymers of acrylic and methacrylic acids |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4066584A (en) |
| GB (1) | GB1529493A (en) |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4179416A (en) * | 1972-11-24 | 1979-12-18 | Avtex Fibers Inc. | Alloy rayon fibers having dispersed therein an amide polymer and a polyacrylic acid salt |
| US4199367A (en) * | 1975-11-07 | 1980-04-22 | Avtex Fibers Inc. | Alloy rayon |
| US4240937A (en) * | 1978-01-03 | 1980-12-23 | Akzona Incorporated | Alloy fibers of rayon and an alkali metal or ammonium salt of an azeotropic copolymer of polyacrylic acid and methacrylic acid having improved absorbency |
| US4242242A (en) * | 1977-06-10 | 1980-12-30 | Akzona Incorporated | Highly absorbent fibers of rayon with sulfonic acid polymer incorporated |
| US4263244A (en) * | 1978-01-26 | 1981-04-21 | Akzona Incorporated | Process for spinning regenerated cellulose fibers containing an alloying polymer |
| US4289824A (en) * | 1977-04-22 | 1981-09-15 | Avtex Fibers Inc. | High fluid-holding alloy rayon fiber mass |
| EP0046157A1 (en) * | 1980-08-15 | 1982-02-24 | Akzona Incorporated | Cellulosic fibers having occluded therein an alkali metal or ammonium salt of a copolymer of polyacrylic and methacrylic acid, process for the manufacture thereof and articles prepared therefrom |
| US4336299A (en) * | 1978-06-24 | 1982-06-22 | Hoechst Aktiengesellschaft | Use of modified cellulose hydrate fibers in the manufacture of bonded non-woven fabrics and products prepared in this manner |
| EP0055056A1 (en) * | 1980-12-22 | 1982-06-30 | Rohm And Haas Company | Alloy rayon fibers of high fluid-holding capacity, method of producing them and manufactured articles comprising them |
| US4356229A (en) * | 1978-12-04 | 1982-10-26 | Rohm And Haas Company | Bonded nonwoven fabrics suitable for diaper coverstock |
| US4575376A (en) * | 1983-11-07 | 1986-03-11 | International Playtex | Method for increasing the absorbency of cellulosic fibers |
| US4657537A (en) * | 1985-05-15 | 1987-04-14 | The Procter & Gamble Company | Disposable absorbent articles |
| US4685909A (en) * | 1985-05-15 | 1987-08-11 | The Procter & Gamble Company | Disposable absorbent articles |
| US4861539A (en) * | 1986-11-20 | 1989-08-29 | Allied Colloids Ltd. | Process of making water-absorbent, water-insoluble, cross linked fiber or film |
| US4871791A (en) * | 1987-04-06 | 1989-10-03 | Hoechst Aktiengesellschaft | Permanently plasticized, cellulose-based product |
| US4910250A (en) * | 1985-06-22 | 1990-03-20 | Hayashikane Shipbuilding & Engineering Co., Ltd. | Aqueous composition, method of producing a water absorbent polymer |
| US4920158A (en) * | 1989-10-11 | 1990-04-24 | Medipro Sciences Limited | Hydrogel-forming wound dressing or skin coating material |
| US4962172A (en) * | 1986-11-20 | 1990-10-09 | Allied Colloids Ltd. | Absorbent products and their manufacture |
| US5013769A (en) * | 1988-08-22 | 1991-05-07 | Medipro Sciences Limited | Method of making a hydrogel-forming wound dressing or skin coating material |
| US5147956A (en) * | 1989-05-10 | 1992-09-15 | Allied Colloids Ltd. | Absorbent products and their manufacture |
| US5280079A (en) * | 1986-11-20 | 1994-01-18 | Allied Colloids Limited | Absorbent products and their manufacture |
| EP0530258B1 (en) * | 1990-05-22 | 1995-09-20 | Sepragen Corporation | Adsorbent medium |
| US5849210A (en) * | 1995-09-11 | 1998-12-15 | Pascente; Joseph E. | Method of preventing combustion by applying an aqueous superabsorbent polymer composition |
| US6565981B1 (en) | 1999-03-30 | 2003-05-20 | Stockhausen Gmbh & Co. Kg | Polymers that are cross-linkable to form superabsorbent polymers |
| EP1997877A1 (en) * | 2006-03-17 | 2008-12-03 | Sanyo Chemical Industries, Ltd. | Cell culture substrate |
| US20090120599A1 (en) * | 2002-01-24 | 2009-05-14 | Hien Vu Nguyen | High absorbency lyocell fibers and method for producing same |
| WO2021168378A1 (en) | 2020-02-20 | 2021-08-26 | Polygreen Ltd. | Multi-layer absorbent product and process for preparing absorbent layer |
| US12129419B2 (en) | 2018-11-13 | 2024-10-29 | Polygreen Ltd | Polymeric composition for use as soil conditioner with improved water absorbency during watering of the agricultural crops |
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|---|---|---|---|---|
| US3256372A (en) * | 1964-04-28 | 1966-06-14 | American Can Co | Method for preparing modified cellulose filter material |
| US3816357A (en) * | 1969-10-24 | 1974-06-11 | American Can Co | Method of preparing an acrylate-polymermodified cellulose fiber |
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| US4179416A (en) * | 1972-11-24 | 1979-12-18 | Avtex Fibers Inc. | Alloy rayon fibers having dispersed therein an amide polymer and a polyacrylic acid salt |
| US4199367A (en) * | 1975-11-07 | 1980-04-22 | Avtex Fibers Inc. | Alloy rayon |
| US4289824A (en) * | 1977-04-22 | 1981-09-15 | Avtex Fibers Inc. | High fluid-holding alloy rayon fiber mass |
| US4242242A (en) * | 1977-06-10 | 1980-12-30 | Akzona Incorporated | Highly absorbent fibers of rayon with sulfonic acid polymer incorporated |
| US4240937A (en) * | 1978-01-03 | 1980-12-23 | Akzona Incorporated | Alloy fibers of rayon and an alkali metal or ammonium salt of an azeotropic copolymer of polyacrylic acid and methacrylic acid having improved absorbency |
| US4263244A (en) * | 1978-01-26 | 1981-04-21 | Akzona Incorporated | Process for spinning regenerated cellulose fibers containing an alloying polymer |
| US4336299A (en) * | 1978-06-24 | 1982-06-22 | Hoechst Aktiengesellschaft | Use of modified cellulose hydrate fibers in the manufacture of bonded non-woven fabrics and products prepared in this manner |
| US4356229A (en) * | 1978-12-04 | 1982-10-26 | Rohm And Haas Company | Bonded nonwoven fabrics suitable for diaper coverstock |
| EP0046157A1 (en) * | 1980-08-15 | 1982-02-24 | Akzona Incorporated | Cellulosic fibers having occluded therein an alkali metal or ammonium salt of a copolymer of polyacrylic and methacrylic acid, process for the manufacture thereof and articles prepared therefrom |
| EP0055056A1 (en) * | 1980-12-22 | 1982-06-30 | Rohm And Haas Company | Alloy rayon fibers of high fluid-holding capacity, method of producing them and manufactured articles comprising them |
| US4575376A (en) * | 1983-11-07 | 1986-03-11 | International Playtex | Method for increasing the absorbency of cellulosic fibers |
| US4657537A (en) * | 1985-05-15 | 1987-04-14 | The Procter & Gamble Company | Disposable absorbent articles |
| US4685909A (en) * | 1985-05-15 | 1987-08-11 | The Procter & Gamble Company | Disposable absorbent articles |
| US4910250A (en) * | 1985-06-22 | 1990-03-20 | Hayashikane Shipbuilding & Engineering Co., Ltd. | Aqueous composition, method of producing a water absorbent polymer |
| US5026596A (en) * | 1985-06-22 | 1991-06-25 | Taiyo Fishery Co., Ltd. | Water absorbent polymer-coated article and method of producing same |
| US4861539A (en) * | 1986-11-20 | 1989-08-29 | Allied Colloids Ltd. | Process of making water-absorbent, water-insoluble, cross linked fiber or film |
| US5280079A (en) * | 1986-11-20 | 1994-01-18 | Allied Colloids Limited | Absorbent products and their manufacture |
| US4962172A (en) * | 1986-11-20 | 1990-10-09 | Allied Colloids Ltd. | Absorbent products and their manufacture |
| US4871791A (en) * | 1987-04-06 | 1989-10-03 | Hoechst Aktiengesellschaft | Permanently plasticized, cellulose-based product |
| US5013769A (en) * | 1988-08-22 | 1991-05-07 | Medipro Sciences Limited | Method of making a hydrogel-forming wound dressing or skin coating material |
| US5147956A (en) * | 1989-05-10 | 1992-09-15 | Allied Colloids Ltd. | Absorbent products and their manufacture |
| US4920158A (en) * | 1989-10-11 | 1990-04-24 | Medipro Sciences Limited | Hydrogel-forming wound dressing or skin coating material |
| EP0530258B1 (en) * | 1990-05-22 | 1995-09-20 | Sepragen Corporation | Adsorbent medium |
| US5849210A (en) * | 1995-09-11 | 1998-12-15 | Pascente; Joseph E. | Method of preventing combustion by applying an aqueous superabsorbent polymer composition |
| US6565981B1 (en) | 1999-03-30 | 2003-05-20 | Stockhausen Gmbh & Co. Kg | Polymers that are cross-linkable to form superabsorbent polymers |
| US20090120599A1 (en) * | 2002-01-24 | 2009-05-14 | Hien Vu Nguyen | High absorbency lyocell fibers and method for producing same |
| EP2263628A1 (en) | 2002-01-24 | 2010-12-22 | McNeil-PPC, Inc. | High absorbency lyocell fibers and method for producing same |
| EP1997877A1 (en) * | 2006-03-17 | 2008-12-03 | Sanyo Chemical Industries, Ltd. | Cell culture substrate |
| US20090136912A1 (en) * | 2006-03-17 | 2009-05-28 | Sanyo Chemical Industries, Ltd. | Carrier for cell culture |
| EP1997877A4 (en) * | 2006-03-17 | 2011-03-23 | Sanyo Chemical Ind Ltd | Cell culture substrate |
| US8148111B2 (en) | 2006-03-17 | 2012-04-03 | Sanyo Chemical Industries, Ltd. | Cell culture carrier comprising poly(meth)acrylic (salt) particle and artificial polypeptide |
| US12129419B2 (en) | 2018-11-13 | 2024-10-29 | Polygreen Ltd | Polymeric composition for use as soil conditioner with improved water absorbency during watering of the agricultural crops |
| WO2021168378A1 (en) | 2020-02-20 | 2021-08-26 | Polygreen Ltd. | Multi-layer absorbent product and process for preparing absorbent layer |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1529493A (en) | 1978-10-18 |
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